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Fatty acids recovery from vegetable oil wet sludge by supercritical alcoholysis
G. Soto, A. Velez, P. Hegel, G. Mabe, S. Pereda ∗
PLAPIQUI, Universidad Nacional del Sur - CONICET, CC 717, 8000 Bahía Blanca, Argentina
a r t i c l e i n f o a b s t r a c t
Article history: In the last decade the production of soybean and sunflower oil has greatly increased worldwide. Together
Received 5 July 2012 with it, the market of the oil refining by-products, phospholipids sludge (wet gum) and distillates of the
Received in revised form 11 January 2013 deodorizer (DDEO) is rapidly changing. In this work, we performed the direct alcoholysis of the phos-
Accepted 12 January 2013
pholipids and oil enclosed in the wet gum using supercritical ethanol. A statistical design of experiments
was carried out to determine the effect of temperature (280–320 ◦ C), ethanol concentration (50–80 wt%),
Keywords:
reaction time (20–50 min) and water content (51–2.4 wt%). In all the cases a complete conversion of
Phospholipids
the lipids was observed. After removal of volatile compounds, the reaction product contained a hexane
Triglycerides
Fatty acids
insoluble solid substrate (around 25%) and an oily phase with more than 50 wt% of fatty esters.
Sludge © 2013 Elsevier B.V. All rights reserved.
Supercritical
Alcoholysis
1. Introduction quality for this purpose due to their low nutritive value (high
water content) compared to gums derived from other vegetable
Methyl and ethyl esters production has nowadays a high indus- oils. Furthermore, sludge processing to recover oil or phospholipids
trial interest because of its direct use as biodiesel. In general, this is complex. Because of its high viscosity and poor flow properties
biofuel is obtained by the transesterification of refined vegetable (sticky behavior), its processing needs large volumes of solvent, and
oils (palm, rapeseed, soybean, etc.) with methanol, in the presence consequently, it is expensive.
of an alkaline catalyst to produce methyl esters and glycerine [1]. In this work, we performed the direct alcoholysis of phos-
Different works in the literature point out that the cost of raw pholipids and vegetable oil (triglycerides) occluded in the wet
material is the major factor affecting the economical viability of gum using supercritical ethanol to produce fatty acids ethyl esters
biodiesel production [2–4]. In this sense, raw vegetable oils, animal (FAEE). The use of soybean and sunflower oil gums (SOGs) as low
fats and waste cooking oils have been proposed as an alternative cost feedstocks can be exploited for biodiesel production. Sun-
triglyceride source for the process [5]. However, biodiesel com- flower oil gums contain approximately ∼45% water, ∼25% oil and
mercial production is currently carried out with alkaline catalysts, ∼30% phospholipids [6]. Therefore, the conventional alkaline pro-
which only achieves high yields when using as the raw-material cess is a non-viable alternative to produce fatty esters from SOGs
refined oil without free fatty acids, phospholipids or water [1]. On [1]. By contrast, the transesterification process by supercritical
the other hand, the extraordinary increase of worldwide produc- alcoholysis is an interesting option for this unconventional and
tion of vegetable oil impacted, not only in the oil market, but also low-cost feedstock [8]. In the supercritical technology, the alcohol
in the oil refining by-products (phospholipids sludge and distil- and lipids, in a molar ratio of 40/1, are heated up to the reac-
lates of the deodorizer) [6]. Even though these residues contain tion temperature (ca. 300 ◦ C) in the absence of catalyst during ca.
high value added products, their cost are decreasing, and they are 20 min and under a pressure range of 100–200 bar [9]. Kusdiana
sometimes becoming a waste, with the related disposal problems and Saka [10] showed that the supercritical alcohol transesterifi-
[7]. Particularly, soy oil has a high concentration of phospholipids, cation allows achieving high conversion even in the presence of
thus an important volume of sludge (also called gums) is being water (up to 36 wt%) and fatty acids (up to 30 wt%) in the pro-
produced. Nowadays, a small fraction of gums is used to recover cess.
high value added products, like lecithin, while most of it is mainly In the present work, a three-variable factorial design of exper-
used as ingredient for animal feed. However, soy gums are of low iments was carried out to study the effects of temperature
(280-320 ◦ C), ethanol concentration (50–80 wt.%) and reaction time
(20–50 min) on the supercritical ethanolysis. Then, a second sta-
∗ Corresponding author. Tel.: +54 2914861700; fax: +54 2914861600. tistical study was implemented at 280 ◦ C to determine the effect
E-mail addresses: spereda@plapiqui.edu.ar, spereda@gmail.com (S. Pereda). of water content on the reaction yield (dehydration up to 35.0
0896-8446/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.supflu.2013.01.003
G. Soto et al. / J. of Supercritical Fluids 79 (2013) 62–66 63
Table 1 Table 4
Characterization of the SOG used in this work: moisture content, hexane- and Statistical analysis of the experimental runs. Average value of the response variables,
acetone- insoluble material, lipid profile. main effects of the studied variables and their quadratic interactions.
Moisture Hexane-insoluble Acetone-insoluble Triglycerides Hexane soluble products (Y1 %) FAEE yield (Y2 %)
(g/kg) material (g/kg) material (g/kg) (g/kg)
Average 77 ± 1 41 ± 1
510 ± 40 4±1 296 ± 62 190 ± 12 Main effects
Temperature (T) 2±2 14 ± 2
Phospholipids Fatty acids (chromatographic area, %) % Ethanol (E) 5±2 11 ± 2
(chromatographic area, %) Reaction time (t) −2 ± 2 8±2
Two factor interaction
PC PE PA PI C16:0–C16:1 C18:0–C18:1–C18:2 T×E 2±2 2±2
58 21 4 17 17 83 T×t −1 ± 2 −4 ± 2
PC, phosphatidyl choline; PE, phosphatidyl ethanolamine; PA, phosphatidic acid; PI, E×t −4 ± 2 2±2
phosphatidyl inositol; C16:0–C16:1, saturated and unsaturated fatty acids of C16,
saturated and unsaturated fatty acids of C18.
The main components identified according to the GC–MS analysis
were ethyl esters and free fatty acids. Also, monoglycerides and
Table 2
GC–MS analysis of the non-volatile and hexane-soluble fraction of reaction products. diglycerides were detected but in minor quantities.
Retention time and relative composition of the products obtained in run N◦ 5.
Table 3
Experimental runs of direct alcoholysis of SOGs (average of two replicates).
Y1 , hexane soluble reaction products; Y2 , FAEE yield; FFA, free fatty acids relative content (areaFFA /(areaFFA + areaFAEE )).
G. Soto et al. / J. of Supercritical Fluids 79 (2013) 62–66 65
Table 5
Influence of drying pretreatment in the supercritical ethanolysis of SOGs.
a significant increment in the FAEE yield. The statistical deviation 3.3. Effects of water and SOG dehydration
and the quadratic interaction (T × E, T × t and E × t) had nearly the
same values, indicating that the quadratic interaction effects were The raw lecithin contains nearly 50 wt% water, which plays an
negligible in the process, from the statistical point of view. important role in the reaction. Previous works showed that the
Fig. 2 shows the FAEE yield as a function of the reaction time for presence of water does not hinder the supercritical transesterifi-
the initial ethanol concentrations (50 and 80 wt%) and both studied cation reaction as it does in the catalyzed synthesis [10]. However,
reaction temperatures (280 and 320 ◦ C). a content of water as high as 50 wt% was not evaluated. On the other
An increase of ethanol concentration and temperature enhanced hand, in this work, a high content of free fatty acid was found in the
the FAEE yield. Indeed, the effect of ethanol concentration was more reaction products. Table 3 shows the relative area (A, %) of free fatty
important at the highest temperature, in which an initial charge of acids to FAEE measured in the product samples.
80 wt% ethanol produced a 55% yield toward FAEE. In general, the lower the FAEE yield, the greater the fatty acids
The temperature effect on vegetable oils transesterification with concentration in the products. Table 3 shows that the content of
supercritical alcohols was previously reported by several authors fatty acids increased at 280 ◦ C, and this increment was even more
[8,9]. For example, Valle et al. [5] showed that the supercriti- significant for the ethanol concentration of 50 wt%. Table 3 also
cal ethanolysis of Raphanus sativus L. oil (reaction time of 15 min reports the initial water to ethanol molar ratio. As can be seen, those
and an ethanol to oil molar ratio of 42) achieved a 95% FAEE runs with high water to ethanol ratio resulted in a final product with
yield at ∼325 ◦ C, while at lower temperatures (∼300 ◦ C) the FAEE higher fatty acids content.
yield diminished to 72%. These observations are in agreement with Since the esterification reaction is also reversible, the presence
results reported in this work. of water pushes backwards the FAEE yield. Therefore, a drying
Furthermore, the molar ratio of alcohol to oil also affects the pretreatment of the raw sludge may be advisable to promote the
reaction. In practice, an excess amount of alcohol is usually used esterification reaction. The original sunflower wet sludge was sub-
to drive the reversible reaction toward the products side and get jected to a drying process at 70 ◦ C in a vacuum oven to reduce the
more FAEE. Pinnarat and Savage [9] showed that increasing the water content of the material to be processed in the supercriti-
molar ratio of alcohol to oil produced a significant enhance in the cal ethanolysis. Two degrees of dehydration were studied, a partial
final ester content. Moreover, Bunyakiat et al. [17] found that the dehydration up to 35 wt% of water and nearly complete drying up
conversion was nearly doubled when the alcohol to oil molar ratio to 2.4 wt%. On the other hand, the ethanol content was kept con-
was augmented from 6 to 42 in the transesterification of coconut stant at the lower value (50 wt%), which means that the ethanol to
oil and palm kernel oil. Higher ethanol to lipid ratio also reduces the lipids molar ratio (ELR) was also reduced. When there is 35 wt% of
critical temperature of the mixture, which allows achieving homo- water in the SOG, the ELR was 28, while for dehydrated SOG (2.4%
geneous reaction conditions at milder temperatures. Hegel et al. humidity), the ELR was 19. As we already mentioned, according to
[18] showed that the critical temperature of mixtures of triglyce- previous results published in the literature, the lower the molar
rides and alcohols decreased from 325 to 300 ◦ C when the molar ratio, the lower the yield toward esters [8,9]. Table 5 shows the
ratio of alcohol to vegetable oil increased from 40 to 50. There- results of the two variable full factorial design of the performed
fore, as more alcohol is fed, higher conversions can be obtained, experiments in which the ethanol concentration and temperature
but eventually a point is reached where more alcohol hinders the were set at 50 wt% and 280 ◦ C, respectively.
reaction kinetics, due to the lipid dilution in the reactants mixture As can be seen in Table 5, the content of free fatty acids in
[18]. In this work, an increment of ethanol concentration from 50 the reaction products was lower in comparison with the previous
to 80 wt% produced an enhancement in the FAEE content, which results, when the water content of the raw material was about
was higher at 320 ◦ C. 50 wt%. This is more significant in the dehydrated SOG (2.4 wt%
humidity), even though in this case the ELR is lower. The reac-
tion products soluble in hexane (Y1 %) have a similar behavior with
respect to the previous experiments. The mean value of hexane-
soluble material was 79 wt%, and both, the water content and the
reaction time, had a low negative influence on it (Table 6).
Table 6
Statistical analysis of the experimental runs with drying pretreatment. Average
value of the response variables, main effects of the studied variables and their
quadratic interactions.
Average 79 ± 1 48 ± 1
Main effects
Reaction time (t) −4 ± 2 3±2
Fig. 2. FAEE yield at different temperatures and ethanol to gum mass ratio. Exper-
Water content (W) −4 ± 2 5±2
imental data: solid symbols 320 ◦ C ((䊉) 80 wt% and () 50 wt%) empty symbols at
Two factor interaction
280 ◦ C (() 80 wt% and () 50 wt%). Lines: sketched for better visualization of FAEE
t×W 1±2 0.3 ± 2
yield trend with operating conditions.
66 G. Soto et al. / J. of Supercritical Fluids 79 (2013) 62–66
4. Conclusions